JPS608697B2 - Polyphosphazene polymers containing cyclic substituents from 1,2- or 1,3-bifunctional compounds - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to polyphosphazene homopolymers and copolymers containing repeat units in the polymer chain and in which cyclic substituents are attached to the phosphorus atom.

More particularly, the present invention relates to polyphosphazene polymers having substituents derived from 112 mono- or 1,3-bifunctional compounds or mixtures that may be present upon substitution of such compounds, and the preparation of such polymers. Regarding the law. Polyphosphazene polymers containing repeating units and having various alkoxy, substituted alkoxy, aryloxy, substituted aryloxy, amino and mercapto groups bonded to scale atoms and methods for producing the same are disclosed in Japan. R
．． Nitrog by Ailcock
en 1 PhoSphor Satoshi Compound
S'', Academic Press, New
York, New York, 1972, and Japan.
R. “Poly(
No. 3,515,799, 3,702,833, 385
No. 6712, No. 39?4242 and No. 4042561
It is described in the number.

Polyphosphazene polymers containing cyclic substituents derived from 1,2- or 113-bifunctional compounds have, to the best of the applicant's knowledge, not been produced by prior art.

US Patent No. 3948 to Reynard et al.
Process for Preparing Copolymers and Turbolimers of Polyphosphazene Polymers Containing Acyclic and Pendant Hydroxyl-Containing Substituents Derived from Monohydroxy-Containing Compounds Such as 82-B, 112-Propanediol and 1,3-Butanediol and Trifluoroethanol It shows. In preparing copolymers and turbolimers such as those disclosed in U.S. Pat. No. 3,948,882, a large excess of all available reactive hydroxy groups is used and no cyclic substituents are formed. The present invention is based on 1.21 and 1.
- It does not produce polymers from 3-difunctional compounds and further monohydroxy compounds. The reason is that the monohydroxy compound reacts preferentially with the backbone of the poly(dichlorophosphazene) polymer and the second hydroxy group of the 112 mono- or 103-bifunctional compound forms a cyclic oxy bond. This is because cyclic substitution would be impossible because it would interfere with the The polymer of the present invention has the formula [wherein x and Y may be the same or different, and 1○-
, -S-, or -NH-; R,
~6 are independently selected from the group consisting of hydrogen, alkyl having 1 to 10 carbon atoms, alicyclic group having 3 to 10 carbon atoms, and substituted or unsubstituted aryl; a is 0 to 1. Contains repeating units.

The polymer may have a solid content of 20 to 5,000 repeating units, such as 20 mm x 50,000. It is understood that the use of only one type of 1,2 mono- or 1,3-bifunctional substituent to prepare the polymers of the present invention will result in a homopolymer.

It is further understood that although it is preferred that all cyclic substituents are the same, different cyclic substituents may be mixed. Cyclic substituent mixtures are different 1, 2, or 1
- It may be a mixed group of 3-1 and 2-functional cyclic groups. The copolymer may have a random distribution of substituents such that X, Y, R, ~6 and a are selected for each polymer unit independently of each other. Polymer, as used herein, refers to both homopolymers and copolymers in which the polymeric units contain more than one substituent.

The polyJ phosphazene polymers of the present invention contain substantially no residual unreacted chlorine, or at least a low amount (lo
Residual chlorine is present in the polymer main chain only at low levels.

Polyphosphazene polymers containing cyclic substituents of the present invention exhibit hydrolytic stability and good thermal stability.

The polymer of the present invention can be used to produce protective films, and can also be used in applications such as molded articles, foams, and coatings.

The polyphosphazene polymer of the present invention has the structural formula -(NPC
12) Reacting a poly(dichlorophosphazene) polymer of n- [wherein n is 20 to 50,000] with a 1.2 mono- or 1.3 monobifunctional compound in the presence of a tertiary amine. Manufactured by

In this case, the 1,2- or 1,3-bifunctional compound may be used alone or during substitution with other 1,2- or 1,2-bifunctional compounds that can react in the same manner as the phosphorus nucleus.
- or 1.3 It can also be used in combination with a monobifunctional compound. 1 Poly(dichlorophosphazene) polymer The poly(dichlorophosphazene) polymer used as starting material in the process of the invention
dichlorophosphazene) polymers are described in U.S. Pat.
No. 05171 and No. 4055520, and the aforementioned date.
R. This is well known as exemplified in Alcock's book.

These polymers have the general formula (NPC12) n-, where n may be from 20 to 50,000 or more.

As described in the aforementioned references, the polymers are often cyclic oligomers, i.e., cyclic trimers and tetramers, having the formula (NPC12)m, where m is an integer from 3 to 7. They are generally produced by thermal polymerization of cyclic oligomers, which constitute up to 90% of the oligomers and in which the ratio of trimer to tetramer varies according to the method of production.

The specific conditions of temperature, pressure and time used for thermal polymerization of cyclic oligomers will vary considerably depending on whether a catalyst is used for the polymerization.

That is, the temperature is about 130 to about 300°C, and the pressure is about 0.1 To
The vacuum to overpressure of less than n and the time can range from 30 minutes to about 48 hours. A suitable method for making poly(dichlorophosphazene) polymers for use in the process of the present invention is described in the aforementioned US Pat. No. 4,055,171.

0 1,2- or 1,3-bifunctional compounds useful in producing the polymers of the present invention Compounds that can be used as substituents in the polyphosphazene polymers of the present invention include those having the formula [wherein X and Y may be the same or different, and 10-"1S
- or -NH-; R and ~6 are independently selected from the group consisting of hydrogen, alkyl having 1 to 10 carbon atoms, alicyclic group having 3 to 10 carbon atoms, and substituted or unsubstituted aryl. and a is 0 or 1].

Difunctional compounds that can be used include; 112-
dihydroxyethane, IG2-dihydroxypropane,
1,3-dihydroxypropane "1,2-dihydroxybutane, 183-dihydroxybutane, 203-dihydroxybutane, 203-dimethyl-213-dihyde.Xybutane"202-diphenyl-143-dihydroxypropane, 2,2-diphenyl-103- Dihydroxybutane, 2,2-dicyclohexyl-103-dihydroxypropane "2,2-dicyclohexyl-1,3-dihydroxybutane, 112-diaminoethane, 102-
Diaminopropane, 1,3-diaminobro/gun, 20
3-diaminobutane, 213-dimethyl-203-diaminobutane, 2,2-diphenyl-113-diaminopro/gun, 212-diphenyl-113-diaminopropane, 202-diphenyl, 113-diaminobutane,
2,2-dicyclohexyl-1,3-diaminobutane,
1,2-dimercaptopro/f, 103-dimercaptopro/f, 113-dimercaptobutane, 2,2-
Diphenyl-113-mercaptopro/gun, 212-
Diphenyl-113-mercaptobutane, 212-dicyclohexyl-1G3-dimercaptobutane, 2,2-
Dicyclohexyl-1,3-dimercaptopro/gun,
1,2-dihydroxychlorohexane, etc.

Bifunctional compounds containing two different reactive groups, such as mercaptoethanol, 1-mercapto-3-pronognol, 3-amino-1-butanol, 2-mercapto-3-aminobutane, 282-diphenyl-1-hydroxy-3 -aminobutane, 212-dicyclohexyl-1-mercapto-3-hydroxybutane, etc. can also be used.

As can be seen from the structural formula, difunctional compounds contain hydroxy, mercapto or amino groups on adjacent carbon atoms or on two carbon atoms separated by one carbon atom.

That is, 203-, 304-1, 405-1, 2.4-, 3G5
-, 4,6-substituted compounds, and comparable functionally substituted compounds are represented by bifunctional structural formulas representing compounds useful in making the polymers of this invention. Therefore, 112-
and 213-difunctionality, as referred to herein, merely represents the relative position of each functional group. Difunctional compounds suitable for the preparation of the polymers of the invention are R
, , R2, and R3 are hydrogen and R4 is a substituent. An example is 112-
Dihydroxypropane "1,2-dihydroxybutane,
102-diaminopropane, 102-dimercaptope.

Including bread etc. 143-Suitable bifunctional compounds are:
R. , R2 and R3 are hydrogen, and R4, R5 and R
This includes compounds where 6 is a substituent.

Examples include 2,2-diphenyl-1,3-dihydroxybutane and 202-diphenyl-103-diaminobutane. Other suitable compounds are 1,3-butanediol,
212-diphenyl-1,3-dihydroxypropaso,
and 203-dihydroxybutane.

Tertiary amine If a tertiary amine is used in producing the polymer of the present invention,
Undesired side reactions are minimized and at the same time it acts as an effective acid scavenger.

The tertiary amines that can be used in the production of the polymers of the present invention are those represented by the general formula It is.

Thus, for example, the tertiary amine may be a trialkylamine such as trimethylamine, triethylamine, triisopropylamine, tri-n-propylamine, triisobutylamine, tri-n-butylamine, and the like. Additionally, tertiary amines containing diamine groups such as pyridine and N.N'N.N'-tetramethylethylenediamine (TMEDA) can also be used. Suitable tertiary amines for use in preparing the polymers of the present invention are triethylamine, N.N.N'.N'-tetramethylethylenediamine, pyridine, N-methylmorpholine; N-methylpyrrole;・4-diaza・1bicyclo(202.2)
Octane (DABCO) and dipiveridylethane.

As mentioned above, the polymers of the present invention are prepared by reacting a poly(dichlorophosphazene) polymer and a 1,2- or 113 monobifunctional compound(s) in the presence of a tertiary amine. Ru.

The reaction conditions and proportions of each component used to make these polymers depend on the reactivity of the difunctional compound used, the tertiary amine used and the degree of substitution desired in the final polymer. I can do it. The degree of substitution in this polymer system is essentially 100%. Generally, the reaction temperature is about 25 to about 20
000 and the time may range from 3 hours to 7 hours.
In this case, the lower the temperature, the longer the reaction time, and the higher the temperature, the shorter the reaction time. These conditions are of course intended to bring the reaction to near completion, i.e. to substantially completely convert the chlorine atoms in the polymer to the corresponding cyclic esters with substituents derived from the difunctional compound. used for. The above-mentioned reactions are usually carried out in the presence of a solvent. The solvent used in the reaction should be a solvent for the poly(dichlorophosphazene) polymer, the difunctional compound and the tertiary amine. Suitable solvents that can be used include diglyme, triglyme, tetraglyme, cyclohexane, chloroform, dioxane,
Contains dioxolane, methylene chloride, toluene, xylene and tetrahydrofuran. The amount of solvent used is not critical and can be used in an amount sufficient to solubilize the reaction mixture materials. Furthermore, the materials within the reaction zone should preferably not contain water. Water in the reaction system must be excluded in order to prevent undesirable side reactions of the chlorine atoms present in the chloropolymer. Preferably the reaction mixture should contain less than 0.01% water. Generally, the amount of difunctional compound used in the present invention should be approximately stoichiometrically equal to the number of chlorine atoms in the polymeric composition.

However, it is preferred to use a slight excess of such compounds in order to completely react all chlorine atoms present. Excesses sufficient to cause acyclic substitution (approximately 2 moles of difunctional compound per mole of chlorine present) should be avoided. Although the cyclic-substituted poly(phosphazene) polymers of the present invention are prepared in the manner described above, ie, in the presence of a tertiary amine, other methods of preparation are possible. U.S. Patent No. 33700 to Alcock et al.
Conventional methods of substitution of poly(dichlorophosphazene), such as by reaction with sodium alkoxide as shown in No. 2P', also derive from difunctional compounds, provided that the reactants are not adversely affected by sodium. Can be used to substitute cyclic substituents. The following examples further illustrate the invention, but are for illustrative purposes and are not intended to limit the scope of the invention. Parts and percentages referred to in the examples and throughout the specification are by weight unless otherwise indicated. Example 1 Polymer Preparation In a 10 oz bottle, 4.0 cc (44 mmol) of anhydrous 1,2-dihydroxybutane, 1 part of anhydrous triethylamine
2.3 cc (88 mmol), 100 cc of anhydrous THF (tetrahydrofuran) and 12.6 cc of poly(dichlorophosphazene). % of tetrahydrolane solution 36.8% (
40.2 mmol) was charged.

This mixture was heated at 8000 °C for 8 hours, the solution was then cooled and the amine hydrochloride was separated from the solution by centrifugation.5 The remainder of the solution was coagulated in hexane to a temperature of 41 °C and Yellow-brown rubbery polymer4.
I got 6 nights. By washing the salt layer with water, an additional 1.0 ta of yellowish brown rubbery polymer was obtained. This polymer was found to have the following analytical values; *triethylamine hydrochloride 1
3.9%, based on 16.1% hydrolyzed chloropolymer in the homopolymer.

Example 2 In a 10 oz bottle, add 2,3-dihydroxybutane 3.
99 cc (44 mmol), anhydrous triethylamine 1
2.3 cc (88 mmol), 0 cc of anhydrous THFIO,
and 12 of poly(dichlorophosphazene).

40 mmol of 67% THF solution was charged.

The mixture was heated to 8,000 hours for 2 hours, followed by coagulation in hexane, yielding 4.39 hours of polymer. Example
3. Into a 10-ounce bottle, 44 mmol of 203-dimethyl-243-dihydroxybutane (5.2 mL), 88 mmol of anhydrous triethylamine, 0 cc of anhydrous THFIO, and 40 mmol of a 12.67% THF solution of poly(dichlorophosphazene) were charged. .

The mixture was heated for 2 hours, followed by coagulation in hexane, yielding 4.3 hours of polymer. Example 4 In a 10 oz bottle, 44 mmol of 212-diphenyl-1,3-dihydroxypropane (10.04 ml), 88 mmol of anhydrous triethylamine, anhydrous THFIO0c
c, and 12.67% of poly(dichlorophosphazene)
40 mmol of THF solution was charged.

This mixture was heated to 80°C. This mixture was subsequently coagulated in hexane to give Tg-9300 and Tg-9300.
A hard white plastic material of 9800 ml was obtained. Example 5 In a 10 oz bottle, 44 ml of 113-dihydroxybutane
mmol (3.95 cc), anhydrous triethylamine 88
mmol, anhydrous THFIOOcc and 40 mmol of a 12.67% THF solution of poly(dichlorophosphazene) were charged.

Claims (1)

[Claims] 1 Formula ▲ Numerical formula, chemical formula, table, etc. ▼ [In the formula, X and Y may be the same or different, and -O-
, -S-, or -NH-; R_
1 to _6 are independently selected from the group consisting of hydrogen, alkyl having 1 to 10 carbon atoms, alicyclic group having 3 to 10 carbon atoms, and substituted or unsubstituted aryl; a is 0 to 1;
w is 20≦w≦50000 per polymer; and X,
Y, and R_1 to_6 are selected for each polymer unit independently of each other. 2. The polymer according to claim 1, wherein X and Y are -O-, a is 0, R_1 is -C_2H_5, and R_2 to_4 are hydrogen. 3 The polymer is 1,3-dihydroxybutane, 2,3-dihydroxybutane, 2,3-dimethyl-2,3-dihydroxybutane, 2,2-diphenyl-1,3-dihydroxypropane, and 1,2-diaminopropane. 2. A polymer according to claim 1, containing a cyclic substituent derived from a compound selected from the group consisting of: 4. The polymer of claim 1, wherein the polyphosphazene polymer has more than one cyclic substituent and the polymer units are randomly distributed. 5 The polymer is 1,2-dihydroxybutane, 2,3-dihydroxybutane, 2,3-dimethyl-2,3-dihydroxybutane, 2,2-diphenyl-1,3-dihydroxy-propane, and 1,2-dihydroxy 5. A polymer according to claim 4, containing an admixture of cyclic substituents derived from compounds selected from the group consisting of probanes. 6 Formula▲There are mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, X and Y may be the same or different, and -O-
, -S- or -NH-; R_1
~_6 are independently selected from the group consisting of hydrogen, alkyl having 1 to 10 carbon atoms, alicyclic group having 3 to 10 carbon atoms, and substituted or unsubstituted aryl; a is 0 to 1; w
is 20≦w≦50000 per polymer; and X, Y
and R_1 to_6 are selected for each polymer unit independently of each other], the formula -(NPCl_
2) a poly(dichlorophosphazene) polymer of __n, where n is from 20 to 50,000, selected from the group consisting of difunctional compounds containing hydroxy, mercapto or amino functional groups or mixtures thereof; A method for producing the polyphosphazene polymer, which comprises reacting the polyphosphazene polymer with a compound in the presence of a tertiary amine. 7 The difunctional compound is 1,2-dihydroxybutane, 2
・3-dihydroxybutane, 2,3-dimethyl-2,3
-dihydroxybutane, 2,2-diphenyl-1,3-
7. The method according to claim 6, wherein dihydroxypropane and 1,2-dihydroxypropane are used. 8. The method according to claim 6, wherein the tertiary amine is triethylamine.